SK278458B6 - 2-(2-subst.benzoyl)cyclohexane-1,3-diones, herbicidal agents on their base and their use - Google Patents

Abstract

The basic subject of the solution described in this patent are 2-(2-subst.benzoyl)cyclohexane-1,3-diones with a general formula (I), where the symbols R and R1 represent hydrogen, alkyl with 1 up to 4 carbon atoms or the group alkyl-OC(O)- with 1 up to 4 carbon atoms in alkyl, the symbol R2 represents halogen or alkoxyl group with 1 up to 4 carbon atoms and the symbols R3, R4 and R5 represent hydrogen, halogen and another different organic rests, explained in the description in more details. This solution also is dealing with the suppression of an unfavourable vegetation with the use of the above mentioned dions and herbicides made based on these diones.

Description

Technical field

The present invention relates to 2- (subst.benzoyl) cyclohexane-1,3-diones, to a method for controlling undesirable vegetation by means of these diones and to herbicidal compositions thereof.

BACKGROUND OF THE INVENTION

In Japanese patent application no. 84632-1974, 10 compounds of the general formula are described

where

X is alkyl, n is 0,1 or 2 and 25

R 1 is phenyl or substituted phenyl as well as an intermediate for the preparation of the active compounds of the general formula

wherein R 1, X and n are as defined above and

R ₂ is alkyl, alkenyl or alkynyl.

In this application, the following are specifically mentioned as herbicidal compounds in which n is 2, X is 5,5-dimethyl, R ₂ is allyl and R 1 is R 1. is phenyl, 4-chlorophenyl or 4-methoxyphenyl.

Intermediates which are precursors of these specifically mentioned compounds have no or almost no herbicidal activity.

The compounds of the invention described below, which are structurally similar to the above compounds, on the other hand, exhibit exceptionally high herbicidal activity. In order to achieve this exceptionally high herbicidal activity, the compounds which form the active ingredient of the herbicidal compositions according to the invention must be substituted in the 2-position of the phenyl radical by chlorine, bromine, iodine or alkoxy, the preferred substituent being chlorine. The exact reason why this substitution confers exceptional herbicidal activity on the compounds is not fully understood.

SUMMARY OF THE INVENTION

The present invention provides 2- (2-substituted-benzoyl) cyclohexane-1,3-diones of formula (I),

where each of the symbols

R ^{@ 1} and R ^{@ 1} are hydrogen, C1 -C4 alkyl or a group of the formula

R’OC (O) where R "represents an alkyl group containing 1 to 4 carbon atoms,

R ² is chloro, bromo or iodo, each of R

R ³ , R ⁴ and R ⁵ independently represent hydrogen, halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, nitro, R ^b SO _n , wherein R ^h is C 1 -C 4 alkyl and n is 0, 1 or 2, a group of the general formula

R ^c CNHO wherein R ^c is C 1 -C 4 alkyl, R ^f C (O) - wherein R ^f is hydrogen, C 1 -C 4 alkyl. 4 alkyl, C 1 -C 4 alkyl or C 1 -C 4 alkyl, a group of the formula -NR ⁸ R ^h, wherein R ⁸ and R ^h each independently is hydrogen or C 1 -C 4 alkyl, wherein R ⁵ also represents trifluoromethyl, and their agriculturally acceptable salts, excluding the compounds of formula (Ia),

(le) where each of the symbols

R and R ¹ is hydrogen or C 1 -C 4 alkyl,

R ² is chloro, bromo or iodo,

R ³ represents hydrogen, iodine or chlorine;

R ⁴ is hydrogen, halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy or nitro.

Most preferably it represents

R ³ chloro, hydrogen, dimethylamino or methoxy,

R ^{4 is} hydrogen, chloro, nitro or SO ₂ CH ₃ a

R ^{5 is} hydrogen.

The structure of the compounds that form the active ingredient of the compositions of the invention can be expressed by the following four structural formulas due to tautometry:

SK 278458 Β6

wherein R, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are as defined above.

The circular proton of each of the four tautomers is rather labile. These protons are acidic and can be cleaved by any base to form a salt whose anion can be expressed by one of the following four resonant formulas:

wherein R, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are as defined above.

Examples of cations of these bases include inorganic cations such as alkali metal cations such as e.g. lithium, sodium and potassium, alkaline earth metals such as e.g. barium, magnesium, calcium and strontium, or organic cations such as e.g. substituted ammonium, sulfonium or phosphonium cations containing aliphatic or aromatic groups as substituents.

As used herein, the term "aliphatic groups" refers, in a broad sense, to a large class of organic groups derived from (1) acyclic paraffinic, olefinic and acetylene hydrocarbons and their derivatives (open chain compounds) or (2) alicyclic compounds. Aliphatic groups may contain 1 to 10 carbon atoms.

The term "aromatic groups" as used herein, in contrast to aliphatic groups in the broad sense 55, refers to groups derived from 1) compounds containing 6 to 20 carbon atoms, characterized by the presence of at least one benzene ring, both monocyclic and and 2) heterocyclic compounds containing 5 to 19 carbon atoms having a similar structure and characterized by the presence of an unsaturated ring system containing at least one atom other than carbon, such as bicyclic and polycyclic hydrocarbons, and derivatives thereof; a nitrogen, sulfur or oxygen atom, and derivatives of these heterocyclic compounds.

Alkyl and alkoxy groups, as defined in the individual symbols in the compounds, include both straight-chain and branched-chain groups. Examples of alkyl include methyl, ethyl, η-propyl, isopropyl, η-butyl, sec-butyl, isobutyl and tert-butyl.

The disclosed compounds, including their salts, which form the active ingredient of the compositions of the invention are active herbicides of a general type, i. are herbicidally active against a wide variety of plant species. In controlling undesirable vegetation, a herbicidally effective amount of the compounds is applied to the area to be suppressed.

The active compounds of the compositions of the invention can be prepared by this general procedure

wherein each symbol has the meaning given above.

Typically, the dione and substituted benzoyl / cyanide are used in a molar ratio and the zinc chloride is used in a slight molar excess. The two reactants and the zinc chloride are mixed in a solvent such as e.g. methylene chloride. A molar excess of triethylamine is slowly added to the reaction mixture with cooling. The mixture was stirred at room temperature for 5 hours.

The reaction product is processed using conventional techniques.

The described substituted benzoyl chloride can be prepared as described by T. S. Oakwood and C. A. Weisgerber, Organic Sznhesis Collected. you. III, p. 122 (1955).

The following example illustrates the synthesis of a representative compound used in the compositions of the invention.

DETAILED DESCRIPTION OF THE INVENTION

Example

2- (2,4-Dichlorobenzoyl) cyclohexane-1,3-dione

1,3-Cyclohexanedione (11.2 g, 0.1 mol), 2,4-dichlorobenzoyl cyanide (20.0 g, 0.1 mol) and anhydrous zinc chloride powder (13.6 g) were mixed in 100 ml of methylene chloride, 0.11 mol). While cooling, triethylamine (10.0 g, 0.12 mol) was added slowly to the reaction mixture. The reaction mixture was stirred at room temperature for 5 hours and then poured into 2N hydrochloric acid. The aqueous phase is discarded and the organic phase is washed four times with 150 ml of 5% sodium carbonate solution. The aqueous washes were combined and acidified with hydrochloric acid and extracted with methylene chloride. The extract was dried and concentrated. 25.3 g of crude product are obtained. The crude product was dissolved in ether and stirred with 250 mL of a 5% copper acetate solution. The resulting copper salt was filtered off, washed with ether and stirred in 6N hydrochloric acid to decompose the salt. The extract was washed with ether to give 22.15 g of the desired product, m.p. 138-140 ° C (yield 77.7%). The structure is confirmed by instrumental analysis.

The following table lists certain selected compounds that can be prepared by the method described. Each compound is identified in the table by a serial number, which is then used to identify it in the rest of the background.

Compound Indole number S R '5 → 1 P or melting point (° C)

15 í H Cl H H 5-Cfij 50 and 65 16 M H Cl H 4-chjo H 79 to 86 17 M The Cl H 4-CH H 60 to 6J 18 H The Cl 3-C1 clay 6-C1 19 The H Cl H B 5-chjo 77 si 80 20 The H Cl 3-C1 B The 60 to 90 21 The H Cl H B 5-m 74 and 75 22 The H Cl H E 5-O ₂ 140 to 14J 23 with H Cl 3-C1 4-C1 H 152 to 154 24 R H Cl 3-C1 4-CH.O H 169 to lft 25 R H Cl H 4-Br Π 104 to 107 26 CH CRJ CK 0 H H R 104 and 108 27 The H Cl H ta) B 29 H R chjo 3-chjo The R 75 and 79 30 H R chjo H R 5-CKjO 89 ei 92 31 B H 9R R 4-CH, 0 5-CKjO 92 to 96 33 ch ₃ CRJ Cl 3-431 4-C1 R 86 p! 89 34 ! H Cl 3-C1 R 5-01 35 C8j CH Cl 3-C1 B 5-C1 105 to 109 36 CH CH Cl 3-Cl 4-01 5-C1 137 to 139 37 H H Cl 3-C1 4-C1 5-C1 106 to 110 38 H H Cl H 4-C1 hl 10B to 111 39 0 WITH Cl H 4-C1 R

CombineBal BB ¹ _h 2 B ³ R * R ⁵ Index or melting point 1 M ^c h Cl 11 The The 1.5613 2 % CM. Cl H 4-C1 H 1.5655 3 -CB "j CL 11 The 6-C1 103 and £ 100 à t! H Cl H 4-Cl The 138 8I 140 5 CLL F-Br 11 Π II e 2-C1 M H 5-C1 74 el 77 7 E H Cl M H I-C 107 et 107 e The The br H B H 93 ei 96 9 E H Cl M n W 79 and 57 10 H H I H H The 66 ei 70 11 H H CL H The 116 Bi 122 12 H H CL The B 5-01 143 and 148 13 H H Cl E with 5-lir 103 ii 115 14 H H [ 3-1 8 164 ii 16?

40 s H Cl H 4-C1 K Chjo-C · <1 CBtCKjlj H Cl H 4-C1 H 41 H Cl 3-C1 4-C1 H 43 H R Cl H 4-F H 44 sodium salt of compound w. 2J 05 al 94 45 Isopropylaonic acid salt of compound no. 23 160 and 1E5 46 triethylammonium salt of compound no. 2] 82 to 85 47 dTBellate salt of compound 6. 23 107 and 106 49 triethanolanonium salt of compound no. 39 4) sodium salt of compound no. 4] 60 to 63 50 CH (CEj) ₂ H Cl 3-OCH. 4-Br H 51 The H Cl H 4-CH.SQ.- H 5! H CH. Cl H 4-C1 H 53 i-CX H Cl H 4-C1 H 54 L-Cjl, and Cl 3-OCR 3 E H 55 CH. CH Cl H 4-CH. SO.- H 5 ' CH Cl J-CH3 4-C1 H 5? H H Cl 3-CH j 4-Cl H 58 H H Cl H 4-C ^-H 59 H H Cl 3-01 rt: ₂ h _{s 2} - H 60 H H Cl H 4-CjH ^SO SO-H 61 H H Cl 3-OCE 4 -CH 2 SO 3 -H 48 and 59 63 CH CH Cl H 1 -n-C 1 H 4 -H semi-solid substance 6] H E Cl 3-C1 4-n-CJ ^ -E 145-143.5 64 H B Cl 3-y ₅ p IC ₂ F ₅ SO ₂ - H oil 65 CH CH Cl H 4-C ^SO SO-H 103 to 103 66 CH CH Cl 3-C1 4-C ₂ H ₅ SO ₂ -H 136 to 111 67 1-C ₇ H ₇ II Cl H 4-C ₂ H ₅ SO ₂ -H brown resin 68 H H Cl 3-C1 4-CH ₂ SO ₂ - H 145 Bi 154 69 ι-ο _Λ H Cl 3-C1 4-CH ₂ SO ₂ - H 70 R H br H 4-CH ₃ CO ₂ - H Brown Resin n H H Cl E I-i ^^ CJR-R 12 H H Cl H 4-CH3S- H 70 and 77 13 H H Cl 3-C1 4-CSjS- H 14 CH ^CH 3 Cl 3-C1 H-CjUjSOj-H 120 to 123 15 H H Cl H 4-dC? 50 ₂ - E 16 CH CH Cl H 4-nC 1 R ₈ SO ₂ -H 77 H H Cl ] -oc ₂ y 4-CH ₂ SO ₂ - H semi-solid substance 78 H H Cl ] -OCH 4-Ε-Ε ₃ φθ ₂ - H golden resin 79 CH CH Cl H i-l 'H-CJH 125 and 12B

* = Description of preparations vwedeoý in the example. q

SK 278458 Β6

As mentioned above, the compounds are prepared by the aforementioned process of phytotoxic substances which are useful in controlling various plant species. Herbicidal activity tests which have been performed using some of these substances are described below.

Preemergence herbicidal test

The day before treatment, the seeds of eight different weed species are sown in loamy-sand soil placed in a test dish. Seeds of one species are sown in each row, parallel to the shorter side of the dish. Seeds of green bar (Setaria viridis) (SV), hedgehogs (Echinochlon crusgalli) (EC), deaf oats (Avena fatua) (AF), tunicate (Ipomoea lacunosa) (IL), abutilone (Abutilon theophrasti) (AT) are used, mustard (Brassica juncea) (BJ), Amaranthus retroflexus (AR), rumex crispus (RC) and chess (Cyperus esculentus) (CE). Sufficient seeds are sown to yield about 20 to 40 seedlings in a row after emergence, depending on the size of the plants.

Weigh 600 mg of the test compound into a piece of glass weighing paper on an analytical balance. The compound paper is placed in a 60 ml clear wide-necked flask and the compound is dissolved in 45 ml acetone or a substitute solvent. 18 ml of the resulting solution is transferred into a 60 ml clear wide-necked flask and diluted with 22 ml of a 19: 1 aqueous acetone mixture containing sufficient sorbitan monolaurate emulsifier to give a final solution of 0.5% (v / v). . The solution is sprayed onto the seed pan using a linear sprayer calibrated to spray the solution at 748 L / ha. The treatment intensity is 4.48 kg / ha.

After treatment, the dishes are placed in a greenhouse where they are maintained at 21.1 to 26.7 ° C. Water is introduced into the bowls by sprinkling. The degree of damage or suppression is determined by comparison with the same plants not treated at the same age two weeks after treatment. The degree of damage is expressed as a percentage of the control of the individual plant species in the range of 0 to 100%, where 0% means that no damage occurred, 100% means that complete damage occurred.

The results of these tests are shown in Table II below.

compound

number SV EC AF IL AT BJ AR RC C R 19 45 60 0 30 40 0 20 60 20 30 85 20 40 95 85 40 45 21 80 10O 0 80 100 100 95 95 22 20 10 0 20 75 30 45 10 23 45 95 10 ABOUT 100 85 iOO 95 24 - 100 0 25 70 90 - iOO 25 - 100 25 80 100 100 - 100 26 40 15 0 □ ABOUT 10 0 30 27 40 80 10 20 60 50 30 75 28 65 75 0 65 100 95 75 55 29 100 95 55 10 80 75 85 95 30 20 20 20 10 40 40 50 20 31 75 95 20 20 100 95 75 10 32 90 85 20 0 iOO 85 75 30 33 80 70 0 40 20 40 90 80 34 60 40 0 20 95 100 100 60 35 0 10 0 0 10 20 20 10 36 ABOUT 0 0 20 100 100 100 0 37 40 0 0 20 iOO 60 90 - 38 10 40 0 20 90 80 20 May 20 39 80 10 about 0 0 0 0 90 40 60 0 0 0 0 0 0 90 41 100 100 85 40 95 iOO iOO 100 42 60 100 25 0 0 0 0 25 43 100 100 45 40 80 90 90 100 44 90 100 0 60 100 100 100 95 45 100 100 0 60 100 100 100 100 46 20 60 0 100 100 100 iOO 20 47 60 70 20 100 100 100 100 60 48 60 0 0 0 0 0 0 40 49 1OO 100 50 1O 60 20 90 100 50 1OO 1OO 80 Io 60 60 90 iOO 51 100 100 90 100 100 100 85 iOO 52 1O0 100 60 1O 100 100 60 100 53 0 20 □ 0 20 20 0 10 54 10 45 10 0 0 0 0 40 55 90 100 60 100 100 100 90 100 56 100 100 80 10 60 60 90 100 57 100 100 90 100 100 100 85 100 58 90 95 0 20 20 40 40 100 59 95 100 85 75 100 100 90 98 60 95 100 50 50 100 100 90 98 61 100 100 75 100 100 100 95 95 62 100 100 95 75 100 100 iOO 80 63 100 100 40 65 100 100 100 95 64 100 100 98 100 100 100 100 90 65 100 100 80 100 100 100 iOO 90 66 100 iOO 75 100 100 100 100 98 73 100 100 60 60 100 100 75 90 74 100 100 70 80 100 100 80 iOO 75 70 100 0 50 100 100 100 80 76 40 90 25 10 100 100 100 10 77 100 100 90 100 100 100 85 - 78 100 100 80 100 100 100 90 -

Table II

Preemergence herbicidal activity

Treatment intensity 4.48 kg / ha

compound

Number SV EC AF IL AT BJ AR RC CE

notes:

a dash means that the seeds of this species did not fit for some reason, an empty space means that the weed plant was not used for testing.

1 1OO 90 20 40 65 50 35 2 80 90 0 30 80 90 20 3 ABOUT ABOUT 0 40 40 40 ABOUT 4 1OO 1OO 50 35 1OO 1OO 90 5 1OO 95 65 35 90 85 50 6 50 25 0 25 100 100 35 7 80 90 1O 60 100 100 100 and 95 95 45 40 100 80 95 9 95 1OO 55 30 1OO 90 iOO 1O 1OO 1OO 60 20 85 1OO 1OO 11 65 1OO 30 40 1OO 100 100 12 65 85 90 75 80 95 90 13 85 75 10 10 85 65 95 14 40 10 bO 0 63 40 65 15 40 60 20 30 iOO 30 75 16 80 60 20 55 75 90 40 17 20 - 10 25 1OO 95 85 18 65 - 30 70 1OO 100 85

SO

ABOUT

1OO

Postemergence herbicidal test

This test is carried out using the same procedure as the preemergence herbicidal test except that the seeds of nine different weed species are sown 10 to 12 days prior to treatment. The water is brought into the treated dish so that it only comes into contact with the soil surface and not with the leaves of the plant shoots.

The results of the post-emergence herbicidal activity test are shown in Table III.

T and B and III

Post-emergence herbicidal activity Treatment intensity 4.48 kg / ha

compound EC AF IL AT BJ AR RC CE 5 number SV 1 60 70 20 40 60 60 35 60 2 30 70 0 50 90 35 30 60 3 0 30 0 70 100 90 55 70 10 4 95 98 20 98 100 100 30 95 5 80 80 75 50 60 80 0 95 6 40 40 10 60 100 100 75 65 7 60 75 40 60 100 75 100 75 6 65 80 75 70 95 BO 90 90 9 85 90 75 70 95 BO 90 90 15 10 95 85 90 60 95 95 60 95 11 50 80 35 55 100 100 95 80 12 45 75 50 55 75 60 50 80 13 30 60 20 60 80 50 60 70 14 20 10 20 50 45 40 40 0 15 65 95 0 65 96 30 100 80 20 16 65 80 20 85 85 30 30 80 17 75 80 30 70 100 100 65 90 18 100 95 10 100 100 100 100 90 19 60 60 40 70 100 75 60 90 20 65 80 10 65 95 95 100 70 21 30 55 ABOUT 80 100 BO 65 80 25 22 0 30 about 20 45 0 30 20 23 85 90 40 85 100 95 100 90 24 0 80 0 70 90 74 - 100 25 100 100 75 90 iOO 100 - 100 26 45 30 0 40 70 65 0 45 30 27 75 80 30 65 50 45 85 85 28 75 60 60 75 100 70 80 25 29 85 85 85 75 85 65 65 85 30 75 50 20 10 0 0 20 40 31 60 60 20 40 40 70 100 40 32 60 25 20 40 90 6? 20 40 35 33 10 0 0 10 10 10 100 40 34 10 10 0 5 50 30 80 0 35 0 0 0 10 60 30 40 0 36 0 0 0 20 20 20 0 0 37 0 0 0 30 40 20 80 0 40 38 10 10 10 20 10 20 20 10 39 40 40 20 0 0 0 5 80 40 90 70 40 20 60 80 20 65 41 60 85 85 20 40 60 103 100 42 60 50 40 70 20 40 60 60 45 43 100 60 30 60 100 100 80 100 44 80 85 0 60 90 90 100 80 45 90 90 10 100 100 100 100 90 46 80 100 0 60 100 100 100 100 47 100 100 0 60 100 100 100 100 50 48 40 40 20 10 10 10 90 40 49 40 40 40 80 100 100 60 60 50 80 60 60 50 50 60 80 70 51 80 80 95 100 100 100 100 90 52 60 60 20 20 40 40 90 60 55 53 10 20 20 0 0 0 0 20 54 20 40 20 5 0 0 0 40 55 40 40 40 60 60 60 80 90 56 80 60 60 50 50 60 80 70 57 80 80 80 95 100 100 100 90 58 60 70 10 70 10 10 20 80 60 65

Example Number SV EC AP ÍL AT BJ AR RC CE 59 100 100 90 100 • 100 100 50 60 100 100 100 100 - 100 100 70 61 90 85 90 85 - 100 100 80 62 100 85 100 75 100 100 100 35 63 70 80 20 100 100 100 35 40 64 75 75 90 70 90 70 40 40 65 100 70 100 55 90 95 100 40 66 100 75 100 90 95 95 100 20 73 100 100 95 100 100 100 55 30 74 100 95 75 100 100 100 85 40 75 100 100 30 95 80 100 80 40 76 Θ0 80 75 75 100 95 95 25 77 80 80 00 90 90 80 90 80 78 80 85 75 85 80 95 100 50

Test of pre-emergence herbicidal effect using multiple weed species.

The pre-emergence herbicidal activity of several compounds was evaluated at a treatment intensity of 2.24 kg / ha against a greater number of weed species.

The procedure is essentially analogous to that used in the preemergence herbicidal activity test and differs therefrom in that only 300 mg of the test compound is weighed in and the treatment intensity is 374 l / ha.

In this test, the bent-tailed flounder (AR) and the juices (BC) are omitted and the following buriant plant species are added:

grassland weeds: Stoklas Bromus tectorum (BT) Perennial Lolium multiflorum (LM) sorghum Sorghum bicolor (SB) Sesbania Sesbania exaltata (SE) nightshade Solanum sp. (SS) candleberry Xanthium sp. (XS)

The test results are shown in Table IV.

T and B and IV

Test of pre-emergence herbicidal effect using multiple weed species

21 Compound number BT SV-EC SB AT BSG IL SE AT SS BJ CE XS

67 20 90 25 98 80 60 90 45 90 45 20 85 65 15 68 65 98 9B 100 100 60 65 100 100 100 80 100 95 100 69 65 100 70 100 100 65 95 100 95 70 65 100 90 - 70 96 100 100 100 100 90 98 90 100 90 60 100 95 80 71 60 20 100 100 100 80 95 35 40 100 20 90 100 40 72 100 100 100 100 100 100 100 100 90 100 60 100 100 20

The compounds of the invention are useful as herbicides, in particular as pre-emergence herbicides, and can be applied by various methods at different concentrations. In practice, the defined compounds are formulated as herbicidal compositions by mixing in an herbicidally effective amount with excipients and carriers which are commonly used to facilitate dispersion of the active ingredients in agricultural applications, taking into account the fact that the method of administration of the toxic agent may have an effect on the activity of that agent in a particular application. Thus, the herbicidally active compounds can be formulated

Granules having a relatively large particle size, for wettable powders, emulsifiable concentrates, dusts, thick suspensions, solutions or any other type of formulation known in the art, depending on the desired mode of application. Compositions for pre-emergence herbicidal applications are wettable powders, emulsifiable centenates, and granules. These compositions may contain from about 0.5% to about 95% by weight, or even higher, of the active ingredient. The herbicidally effective amount depends on the type of seeds or plants to be controlled and the degree of treatment varies from about 0.056 to about 28.0 kg / ha, preferably from about 0.11 to about 11.2 kg / ha.

The wettable powders are in the form of finely divided particles which readily disperse in water or other dispersants. The wettable powders are applied to the soil either in the form of a dry powder or in the form of a dispersion in water or other liquid. Typical carriers for wettable powders are Valcar mixture, kaolin clays, various types of silica and other readily wettable organic and inorganic diluents. Typically, wettable powders are formulated to contain from about 5 to about 95% of the active ingredient, and usually also contain small amounts of wetting, dispersing or emulsifying agents to facilitate wetting and dispersion.

Emulsifiable concentrates are homogeneous liquid compositions which are dispersible in water or other dispersing agents and may consist either solely of a mixture of the active compound with a liquid or solid emulsifier, or may also contain liquid carriers, such as e.g. xylene, heavy aromatic gasoline. isophorone and other non - volatile organic solvents. Prior to herbicidal application, these concentrates are dispersed in water or other liquid carrier and are usually applied to the treatment area as a spray. The percentage by weight of the principal active ingredient may vary depending on the manner in which the composition is to be applied, but typically such herbicidal composition will contain about 0.5 to about 95% by weight of the active ingredient.

Granular compositions in which the toxic substance is applied to relatively coarse particles are usually applied to the area in which the desired vegetation control is to be achieved, without dilution, the typical carriers for granular compositions being: sand, valcar mix, bentonite clays, vermiculite, perlite and other organic or inorganic substances which have an absorbent capacity or which can be coated with a textile substance. Generally, the granular compositions are made to contain about 5 to about 25% by weight of the active ingredients, which may include surfactants such as e.g. aromatic naphtha, kerosene or other petroleum fractions, or vegetable oils and / or thickeners, e.g. dextrins, glues or synthetic resins.

Typical wetting, dispersing or emulsifying agents used in agricultural compositions are, for example, alkyl and alkylarylsulfonates and sulfates and their sodium salts, polyhydric alcohols, and other types of surfactants, many of which are commercially available. When surfactants are used, these generally comprise about 0.1 to about 15% by weight of the herbicidal composition.

Dusts, which are free-flowing mixtures of active ingredients with finely divided solids such as talc, clays, flours and other organic and inorganic solids, which serve as dispersants and carriers for the toxic substance, are useful compositions for application to the soil.

For specific purposes, pastes are used, which are homogeneous suspensions of finely divided solid toxic substances in a liquid carrier, such as e.g. in water or oil. These compositions usually contain from about 5 to about 95% by weight of the active ingredient and may also contain small amounts of wetting, dispersing or emulsifying agents to facilitate dispersion. Prior to application, the pastes are usually diluted and applied to the treatment area in the form of a spray.

Other useful compositions for herbicidal applications are simple solutions of the active ingredient in a dispersing medium in which the active ingredient is completely soluble at the desired concentration. Examples of suitable dispersing agents are acetone, alkylated naphthalenes, xylenes and other organic solvents. Pressurized sprays can also be used, typically aerosols, in which the active ingredient is dispersed in fine form due to the evaporation of the low boiling solvent carrier which constituted the dispersing medium, such as freon.

The phytotoxic compositions of the invention are applied to plants by conventional methods. Dusts and liquid compositions can be applied to plants using a variety of hand or powered dusting and spraying devices. Since they are also effective at very low doses, the compositions according to the invention can also be applied as aircraft dusts and sprays. As a typical example, when modifying or inhibiting the growth of germinating seeds or emerging seedlings, dusts or liquid compositions are applied to the soil by conventional methods and distributed in the soil so as to reach at least about 1.25 cm below the soil surface. It is not necessary to mix phytotoxic agents with the soil particles, but they can be applied by simple spraying or sprinkling of the soil surface. The phytotoxic compositions of the invention may also be applied by adding them to the irrigation water supplied to the field to be treated. This method of application allows the compositions of the invention to penetrate the soil along with water absorption. Dusts, granular compositions or liquid compositions applied to the soil surface can be subdivided below the soil surface by conventional techniques such as e.g. disc, hinder or mix.

The phytotoxic compositions of the invention may also contain other additives, for example fertilizers, other herbicides and other pesticides, used as adjuvants or in conjunction with any of the aforementioned adjuvants. Examples of other phytotoxic compounds which may conveniently be used in combination with the disclosed compounds include, for example, anilides such as e.g. 2-benzothiazol-2-yloxy-N-methyl-acetanilide, 2-chloro-2 ', 6'-dimethyl-N- (n-propylethyl) acetanilide, 2-chloro-2', 6-diethyl-N- (butoxymethyl) ) acetanilide; 2,4-dichlorophenoxyacetic acid, 2,4,5-trichlorophenoxyacetic acid, 2-methyl-4-chlorophenoxyacetic acid and their salts, esters and amides; triazine derivatives such as 2,4-bis (3-methoxypropylamino) -6-methylthio-s-triazine; 2-chloro-4-ethylamino-6-isopropylamino-striazine and 2-ethylamino-4-isopropyl-amino-6-methylmercapto-s-triazine, urea derivatives such as e.g. 3- (3,5-dichlorophenyl) -1,1-dimethylurea and 3- (p-chlorophenyl) -1,1-dimethylurea and acetamides; such as N, N-dialyl-α-chloroacetamide and the like; benzoic acids such as 3-amino 2,5-dichlorobenzoic acid; thiocarbamates such as e.g. S- (1,1-dimethylbenzyl) piperidene-1-carbothioate, 3- (4-chlorophenyl) methyldiethylcarbothioate, ethyl 1-hexahydro-1,4-azepino-1-carbothioate, S-ethylhexahydro-1H-azepine-1 -carbothioate, S-propyl-N, N-dipropylthiocarbamate,

SK 278458 Β6

S-ethyl-N, N-dipropylthiocarbamate, S-ethylcyclohexylethylthiocarbamate, S-ethylhexahydro-1H-azepine-1-carbothioate and the like; anilines such as e.g. 4- (methylsulfonyl) -2,6-dinitro-N, N-substituted aniline, 4-trifluoromethyl-2,6-dinitro-N, N-di-n-propylaniline, 4-trifluoromethyl-2,6-dinitrone -ethyl-n-butylaniline, 2- [4- (2,4-dichlorophenoxy) phenoxy] propanoic acid, 2- [1- (ethoxyimino) butyl] -5- [2-ethylthio) propyl] -3-hydroxy- 2-Cyclohexen-1-one, (±) -butyl-2- [4 - [(5-trifluoromethyl) -2-pyridinyl) oxy] phenoxy] propanoate, sodium 5- [2-chloro-4- (trifluoromethyl) phenoxy] -2-nitrobenzoate, 3-isopropyl-1H-2,1,3-benzothiadiazin- (4 (3H) -one-2,2-dioxide and 4-amino-6-tert-butyl-3- (methylthio)) -s-triazin-5 (4H) -one or (4-amino-6- (1,1-dimethylethyl) -3- (methylthio) 1,2,4-triazin-5 (4H) -one and S- ( O, O-diisopropyl) benzenesulfonamide.

Fertilizers which may conveniently be used in combination with the active ingredients of the compositions according to the invention include, for example, ammonium nitrate, urea and superphosphate. Other useful ingredients are substances in which plants are rooted or grown, such as compost, manure, humus, sand, and the like.

Claims (20)

1. 2- (2-Substituted benzoyl) cyclohexane-1,3-diones having the general formula (I), wherein each of the symbols R ^{@ 1} and R ^{@ 1} are hydrogen, C1 -C4 alkyl or a group of the formula ROC (O) wherein R ^a represents an alkyl group having 1 to 4 carbon atoms, R ² is chloro, bromo or iodo, each of R R ³ , R ⁴ and R ⁵ independently represent hydrogen: halogen; (C 1 -C 4) alkyl, (C 1 -C 4) alkoxy; nitro; R ^b SO _n wherein R ^b is C 1 -C 4 alkyl; and n is 0,1 or 2; a group of the general formula; wherein R ^c is C 1 -C 4 alkyl; R ^f C (O) -, wherein R ^f is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl or C 1 -C 4 alkoxy; a group of the formula -NR ⁸ R ^h wherein R ^g and R ^h each independently is hydrogen or C 1 -C 4 alkyl, wherein R ⁵ also represents also triíluórmetylskupinu; and their agriculturally acceptable salts, excluding the compounds of formula (Ia), where each of the symbols R and R ¹ is hydrogen or C 1 -C 4 alkyl, R ² is chloro, bromo or iodo, R ³ represents hydrogen, iodine or chlorine; R ⁴ is hydrogen, halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy or nitro. 2. 2- (2-Substituted benzoyl) cyclohexane-1; The 3-dione of claim 1, wherein each of the symbols R and R ¹ is hydrogen or C 1 -C 4 alkyl, R ² is chloro, bromo or iodo, each of R R ³ , R ⁴ and R ⁵ independently represent hydrogen; halogen; (C 1 -C 4) alkyl; (C 1 -C 4) alkoxy; nitro; R ^b SO _n wherein R ^b is C 1 -C 4 alkyl; and n is 0, 1 or 2; a group of the general formula wherein, R ^c is C 1 -C 4 alkyl; R ^f C (O) -, wherein R ^f is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl or C 1 -C 4 alkoxy; a group represented by the formula -NR ⁸ R ^h , where R ⁸ and R ^h independently represent hydrogen or C 1 -C 4 alkyl, in addition R ⁵ is trifluoromethyl; and the agriculturally acceptable salts thereof, excluding the compounds of formula (Ia) as defined in claim The 2- (2-substituted-benzoyl) cyclohexane-1,3-dione of claim 1, wherein each of R 1 and R ¹ are hydrogen or methyl, R ² is chloro; R ³ is hydrogen, chlorine, dimethylamino or methoxy, R ⁴ is hydrogen, chloro, nitro or a group of the formula SO ₂ CH ₃ a R ⁵ represents hydrogen, and agriculturally acceptable salts thereof, excluding the compounds of formula (Ia) as defined in claim 1. The 2- (2-substituted-benzoyl) cyclohexane-1,3-dione of claim 3, wherein each symbol is as defined in claim 3, wherein R ³ is bonded at the 3-position, R ^{4 is} at the 4-position, and substituent R ⁵ at the 5 or 6 position, and agriculturally acceptable salts thereof, excluding the compounds of formula (Ia) as defined in claim 1. SK 278458-6 The 2- (2-substituted-benzoyl) cyclohexane-1,3-dione of claim 3, wherein each of R ¹ and R ¹ is hydrogen, R ² is chlorine, R ³ is hydrogen, 3-chloro, 4-methoxy or 3-dimethylamino and R ⁴ is 4-chloro, or 4-CH ₃ SO ₂ - and R ⁵ is hydrogen, and agriculturally acceptable salts thereof, excluding the compounds of formula (Ia) as defined in claim 1. The 2- (2-substituted-benzoyl) cyclohexane-1,3-dione of claim 2, wherein R ² is chlorine and the other symbols are as defined in claim 2, and agriculturally acceptable salts thereof, excluding the compounds of formula (I). 1a) as defined in claim 1. 7. 2- (2-substituted benzoyl) -cyclohexane-l, 3-diones according to claim 1, wherein R is methyl, ^R1 is methyl, ^R2 is chloro, ^R3 is hydrogen, ^R4 is hydrogen and ^R5 is 6-chloro, and their agriculturally acceptable salts, excluding the compounds of formula (Ia) as defined in claim 1. The compound according to claim 1, wherein R is hydrogen, R ¹ is hydrogen, R ² is chlorine, R ³ is hydrogen, R ⁴ is hydrogen and R ⁵ is hydrogen. 6-chloro, and their agriculturally acceptable salts, excluding the compounds of formula (Ia) as defined in claim 1. The 2- (2-substituted-benzoyl) cyclohexane-1,3-dione of claim 1 wherein R is hydrogen, R ¹ is hydrogen. R ² is chlorine, R ³ is hydrogen, R ⁴ is 4-chlorine and R ⁵ is hydrogen, and agriculturally acceptable salts thereof, excluding the compounds of formula (Ia) as defined in claim 1. 10. 2- (2-substituted benzoyl) -cyclohexane-l, 3dióny according to claim 1, wherein R is H, ^R1 is H, ^R2 is chlorine, ^R3 is 3-chloro, R ⁴ is H and R ⁵ is 6-chloro and their agriculturally acceptable salts, excluding the compounds of formula (Ia) as defined in claim 1. 11. 2- (2-substituted benzoyl) -cyclohexane-l, 3-diones according to claim 1, wherein R is hydrogen, ^R1 is hydrogen, ^R2 is chloro, ^R3 is hydrogen, ^R4 is hydrogen and ^R5 is 5-trifluoromethyl, and agriculturally acceptable salts thereof, excluding the compounds of formula (Ia) as defined in claim 1. 12. 2- (2-substituted benzoyl) -cyclohexane-l, 3-diones according to claim 1, wherein R is H, ^R1 is H, ^R2 is chlorine, ^R3 is 3-chloro, R ⁴ is 4-chloro and R ⁵ represents hydrogen, and agriculturally acceptable salts thereof, excluding the compounds of formula (Ia) as defined in claim 1. 13. 2- (2-substituted benzoyl) -cyclohexane-l, 3-diones according to claim 1, wherein R is H, R ¹ is hydrogen, R is chloro, R ³ is 3-chloro, R ⁴ is 4-methoxy and R ⁵ represents hydrogen, and agriculturally acceptable salts thereof, excluding the compounds of formula (Ia) as defined in claim 1. 2- (2-Substituted benzoyl) cyclohexane-1,3-diones according to claim, wherein R is hydrogen, R ¹ is hydrogen, R ² is chlorine, R ³ is hydrogen, R ⁴ is 4-bromo and R ⁵ represents hydrogen, and agriculturally acceptable salts thereof, excluding the compounds of formula (Ia) as defined in claim 1. 15. A compound according to claim 1, wherein R is isopropyl, R &lt; ¹ &gt; is hydrogen, R &lt; ² &gt; is chlorine, R &lt; ³ &gt; is hydrogen, R &^lt; 4 &gt; ⁵ represents hydrogen, and agriculturally acceptable salts thereof, excluding the compounds of formula (Ia) as defined in claim 1. 2- (2-Sub-benzoyl) cyclohexane-1,3-diones according to claim 1, wherein R is isopropyl, R ¹ is hydrogen, R ² is chlorine, R ³ is 3-CH 3, R ⁴ is 4-CH 3 SO ₂ and R ⁵ represents hydrogen, and agriculturally acceptable salts thereof, excluding the compounds of formula (Ia) as defined in claim 1. 17. 2- (2-substituted benzoyl) -cyclohexane-l, 3-diones according to claim 1, wherein R is H, R ¹ = H, R ² = Cl, R ³ is hydrogen, R ⁴ is 4-CH ₃ SO ₂ and R ⁵ represents hydrogen, and agriculturally acceptable salts thereof, excluding the compounds of formula (Ia) as defined in claim 1. 18. 2- (2-substituted benzoyl) -cyclohexane-l, 3-diones according to claim 1, wherein R is H, ^R1 is H, ^R2 is chlorine, ^R3 is 3-chloro, R ⁴ is 4-chloro and R ⁵ represents hydrogen, in the form of the sodium, isopropylamine, triethylammonium or potassium salt, excluding the compounds of formula (Ia) as defined in claim 1. A method for controlling undesirable vegetation, characterized in that a herbicidally effective amount of 2- (2-subst.benzoyl) cyclohexane-1,3-dione according to any one of claims 1 to 18 is applied to the area to be suppressed. . A herbicidal composition, characterized in that it contains at least one 2- (2-substituted-benzoyl) cyclohexane-1,3-dione as an active ingredient according to any one of claims 1 to 18.